Material for the production of multicolor photographs



Feb. 9, 1943.

a. GASPA MATERIAL Fon THE PRODUCTION oF MULTIcoLoR Pacnoemfns Filed May 27. 1959 /fj lllllllllllllllllllllllllllllllllllllllllllllllllllllllii Anaval-ww; orso fume we Mann/654m@ (IAL/df /Suvcnfor Patented Feb. 9, 1943 OFFICE MATERIAL Fon THE PRODUCTION or MULTIooLoRl PHOTOGRAPHS Bla Gaspar: "Hollywood, Calif., assignor to Chromogen, Incorporated, a

Nevada corporation of Application May 27, 1939, Serial No. 276,238l In Great Britain June 14, v1938 4 Claims. (Cl. 95-2) It is already known from my prior patents that a photographic dye-image may be produced by local dye destruction in a layer containing dyes or dye-forming substances and being in immediate contact with an uncolored` layer contain-v ing a photographic silver image. The present invention relates to improvements in this process and to materials useful therein:

It has been found that when the process is used to obtain` dye-images in a multi-layer material, diiculties are encounteredin connection with the exposure of the dierent layers and it is'one of the objects Vof the invention to provide multilayer materials for three-color photography which arefespecially adapted to the above mentioned process. Further objects of the invention will be apparent from the description:

If the process is used-for the production of three color pictures, a taking material is used which comprises a front layer, sensitive topblue light, a yellow dyed filter layer arranged immediately behindthe frontlayer, and further lightsensitive silver halide emulsion, layers, one of which is sensitized to green and the other one of which is sensitized to red. The'yellow dye ,in the filter layer `is resistant to the ordinary photographic treating solutions but is capable of being locally destroyed under the control of the photographic silver image when treated after development by the treating solutions known for this process. The supportr a color- 1 the yellow dye image underA the control of the silver image present in the preceding layer, but to produce also the second dye image or all of the dye images from pre-dyed layersunder the control of the silver deposit present in the immediately preceding silver halide layer. For this purpose a light-sensitive m'aterial is used in which pre-dyed colored layers, which are free from light sensitive silver salts, are combined with light-sensitive silver halide layers and ar\ v ranged in such a manner that behind the blueless separating layer is arranged between the f When a material of The other two light-sensitive layers stances' and this may be done by the process of my prior Patent No. 2,071,688, dated February. 23, 1937. The dye image corresponding to the silver imageproduced lin the rear layers of the I material may also be formed by dyes present in 4'the light-sensitive layer itself and in this case the dye present in the rear layer should have a flower bleaching speed than the yellow dye used fior the production` of the yellow part-image.

- Furthermore, it is possible to producenot only sensitive layer a yellow colored colloid layer,` behind the red-sensitive layer ablue-green colored colloid layer, and behind the green-sensitive layer a magenta-dyed colloid layer isarranged, .layers of plain gelatin separating each. colored glayer from the followinglight-sensitive layer.

In the drawing I have .illustrated various-exemplications of my invention. Fig. l-shows an arrangement of light sensitive layers and intimately associated dyed gelatine layers, in which the material can be exposed from the side of the blue sensitive layer, to all of the threeprimary colors'of the spectrum. Fig. 2 shows a different arrangement, adapted for printing, in which the green sensitive layer and the blue sensitive layer can be exposed from one side, and the other blue sensitive layer can be exposed from the other side.

For instance, in Fig. 1 the iront layer of the light-sensitive material' consists of an ordinary blue-sensitive emulsion. This emulsion should bea ne grain emulsion and the layer should be thinner than the usual negative layers. Behind the layer a yellowecolored gelatin layer is arranged which contains aneasilyy destroyable azo dye such as, for instance, Chrysophenine G (Schultz Farbstoiftabellen, Leipzig, 1931,-7th ed., vol. 1, No. 726) in a concentration oi 2 grams per sq. m.l The followingflayeur is a thin layer of plain gelatin and this is followedA by a greensensitive silver halide layer in front'of a gelatin layer colored with about 1 gram per sq. m. of the magenta dye Anthosine BN (Fierz-David, Kuenstliche Organische Farbstoil'e, Berlin 1926, Vol. III, page 663). Between the magenta'layer and the followingv red-.sensitive silver halide layer there is coated a layer oi plain gelatin, and behind the red-sensitive layer there is arranged a blue-green colored gelatin layer containing 0.3

and I-aminO-Z- nphthol ethyl ethervwith sodium nitrite and hydrochloric acid, isolating the interl ment and after fixing, the 111m is treated by one ture with waterto a solution of 1-acety1amino-8- L naphthol3,6disulphonlc acid which` has been made alkaline by addition ot sodium bicarbonate l and to which pyridine has been added). The dye may be precipitated by calcium salts or salts of i acidez?" mediate product formed and adding it in admix-V 'present in one or more of the light-sensitive layers as shown, or in the colloid layers. The folf lowing table contains someoi.' the various possibilities of combining the different layers, and' 5 Example 1 represents the arrangement shown in Fig. 2.

Colm-of the colored layers and senfsivitg of the silver halide layers respectively Seqqfrgf th@ Example i Example 2 Example 3u Example 4 Example 5 Example 6 Gelatin layer Blua-green Magenta Yellow: Blue-green Magenta.--; Yellow. Sliver halide B1ue-sensitive..--. Blue-sensitive. Green-sensitive.... Bluesonsitive-.... Blue-sensitiv Green-sensitive.

yer. Do Green-sensitive Red-sensitivecon- Red-sensitive con- Green-sensitive Red-sensitive con- Red-sensitive.

. con yeyellow tainingrediilter containing yeltaining ye ow I low filter dyn. iilter ye. dye. low iilter dye. iiltor dye. Gelatin layer ellow ow Magenta M lue-green Blue-green.

Do Magenta Blue-green Bl n Yellow Yellow Magenta. Silver halide Wh te or colored White or colored Green orredsensi- White or colored Blue sensitivc....- Green orred sensilayer. light. light. light. t tive.

organic bases. The support may be situated in In silver` halide layers are to be exposed during front of the blue-sensitive layer or behind the blue-green colored rear layer as shown,` or the support may replace one of the colorless intermediate layers. 'llhe thickness of the colored gelatin layers may be. adjusted to the diierent bleaching speeds of the dyes as described hereinafter. After the exposure of the material in a camera with the blue-sensitive layer facing the lens, the silver images are produced by develop-V of the known dye-destroyingsolutions which, as described and claimed in my Patent 2,221,793 of Nov. 19, 1940, should contain an accelerating substance. Afterthe removal of any remaining silver, a dye image in natural colors is obtained. This "dye image may be printed on a printing material of the same general kind but the concentration of the dyes in the printing material should rbe lowered if the printing layers are applied to an opaque support for the production of color prints on paper or the like. The printing material is exposed behind the colored original and processed in substantially the same manner.

If the material is used as a printing material and has a transparent support as, for instance, in the production of' kinematographic illmsfa sound image may be printed into the light-sensitive layers for the production of a colored sound record or for the production of a black silver sound record. i

In Fig. 2 is shown another multilayer material especially adapted to the production of three-color-prlnts accordmg to the process of the the invention. It comprisils three light-sensitive layers which aresensitized and'combined with three colored colloid layers in such a manner that each sensitive layer can be individually printed by colored printing light. 'I'hel sequence of the superimposed, light-sensitive layers and the colored layers iss'uch that one outside layer is a colored layer .whereas the oppositeoutside layer is a. light-sensitive layer. Behind the colored outside Vlayer there are arranged two light-sensitive layers, and behind the sensitive layer situated on the other outside there are arranged the remaining two colored layers. The support of the layers may be situated in such a manner as to separate the two neighbouring light-sensitive' layers or the two neighbouring coloredlayers as shown.' Alternatively, the support may be situated behind one of the outside' layers. The dyes used ,forcoloring the .colloid layers are a yellow dyeI 4a magenta dye and a blue-green dye. and the dyes referred to above may' be used. Removable'iilter dyesmay be 75 the above examples. the two consecutive printing from the direction of the colored outsituated on the other outside surface is exposed to printing light from this side'. It is also possible to expose two layers from the side carrying the single emulsion layer and in this case it will be necessary to alter the sensitivity of the layers and possibly also to add illter dyes into the lightsensitive layers or to add an additional illter dye into the colored "layers, Separate lter, layers l may be used between the sensitized layers. If

all of the layers are to be printed upon from one f side, the rear layer should be sensitive to in- 35 frared light.

The printing material is printed behind black and white positive partiimages or behind multicolormaster positives of the well known kind. Each color selection positive is printed upon that light-sensitive layer which is adjacent 'to lche layer colored complementary to the color sensation recorded in the partial positive. Thus, for example, the green color selection positive is used for printing on to the light-sensitive layer adjacent to the magenta dyed layer.

After the development ofthe silver images the whole material is treated with a dye destroying solution which may contain an accelerating substance in addition to the dye destroying agent.'

In a multilayer material of the kind described it is sometimes diiilcult to select dyes having equalbleaching speeds, when treated with the same bleaching agent. 'Ihis different behaviour results in shortcomings in the iinal multicolon picture.

In order to remedy this deiiciency, the thick. ness of the individual layers of the multilayer material are adjusted to the bleaching speed of the dyes present therein.

The proportion of the thicknesses of the layers may be -approzdmately arrived at in the following manner.

It," for instance, a yellow dye, a magenta dye and a bluegreen dye are to be used, and if to obtain a neutral grey, the dye concentrations of the three dyes have to be in the proportion of 2 gramszl gram:0.3 gram per square Vmetre respectively, then three dye solutions will be presensitive layers.

WW... pared containing the/iid quantities or yenow. magenta andbluegreen dye in the same amount of gelatin/.vf :Equal volumes of the three dyed gelatinsolutions are coated on equal surfaces of photographic layers containing a uniform silvei deposit oi' equal density, the thickness of the dyed layers thus being practically equal. A

Several samples o! the three differently colored materials are now treated with the dyedestroying agent for say l0, 20, 30, 40, 50 and 60 minutes. Alter removal of the residual silver Y it may be found, for instance, that neutral grey will be obtained by superposing the sample of f' the yellow material treated for 30 minutes on the magenta sample that was treated for-20 minutes and on. the bluegreen sample that was-treated Ior 60 minutes. Then it follows that-the .bleaching times are in the ratio of 30:20:60, and the thicknesses o! the layers containing the said dyes should be approximately in the proportion of Anl/2: V6 or 2:3:1, and hence the layers should be prepared by adding 2 grams of the yellow dye to two volumes of gelatin solution, l gram of the magenta dye to 3 volumes o! gelatin solution and 0.3 gram of the bluegreen dye to 1 volume o! the gelatin solution. It the colored gelatin solutions thus prepared are Aamplied to l sq. m. oi the material, each one in direct contact with a sensitized silver halide layer, andeach pair of. ldyed `and silver halide layers Vpossibly being separated from adjacent ,pairs of layers by a thin` layer oi gelatin, lthen the diil'erent bleaching speeds of the dyes will be compensated to a great Differences may. however, result for example from the fact that thev action of the treating solutions onthe inner layers begins later than on the surface layer. The allowance for this diierence may be arrived at by test 'and trial.A

ing three selectively sensitive silver halide emulsion layers and three colored layers which are not light-sensitive, each oi said colored layers being arranged in immediate contact with only one of the light-sensitive layers and being dyed with a reducible dye resistant to ordinary photographic treating solutions and capable of being locally destroyed under the influence of a metallic silver image, the layers being so arranged that one outside layer is iormedby a layer sensitive to. blue light behind which there are arranged two of the colored layers at least one of which is absorbent for blue light, whereas the other4 outside layer is formed by the third colored layer behind which there are arranged the other two light-sensitive layers.

3. A light-sensitive multilayer material for the production or photographic dye images. comprising three selectively sensitive silver halide emul- 'sion layers and three colored layers which are not'light-sensitive, each of said colored layers being arranged in immediate contact with only one of the iight-sensitive layers and being dyed with a reducible dye resistantto ordinary photo-'l graphic treating solutions and capable of being locally destroyed under the influence or a metallic silver image, the layers being so arranged- 5 that one outside layer is formed by a light-sensit extent by the differente in the thicknesses or the 1. A light-sensitive multilayer material for the tlve layer behind which there are arranged two ,oi the colored layers. whereas the other outside layer ls-formed by the thirdeolored layer behind which there are arranged' the other two lightroithe l2. light-sensitive multilayer material production vof photographic dye images, compristive layer behind which therev are arranged two ofthe colored layers, whereas the other outside layer is formed by the third colored layer behind which VAthere are arranged the other two lightsensitive layers, said third-colored layer' being transmittant for blue light and one of the two light-sensitive layers arranged behind the third colored layer containing a yellow illter dyestuil.

fl. A light-sensitive multilayer material for the production of photographic dye images, comprising three selectively sensitive silver halide emulsion layers and three colored layers which are not light-sensitive,l each of said colored layers l being arranged in immediate contact with only one of the light-sensitive layers and being dyed with a reducible dye resistant to ordinary photngraphic treating solutions and capable of being locally destroyed under the iniluence oi a metallic silver image, the layers being so arranged that one outside layer is formed by a layer-sensitive to blue light behind which there are ar'- ranged two of the colored layers at least one of which is absorbent for blue light, whereas the other outside layer is formed by the third colored layer behind which there are arranged the other two light-sensitive layers, said third colored layer being transmittant tor-blue light and one o! the two light-sensitive layers arranged behind the third colored layer containing a yellow 'illter am aAi'suAn.l 

